EP2110405A1 - Stabiliser systems for polymers containing halogen - Google Patents

Abstract

Stabilizer system comprises an alkali-earth-double carbonate-chalk compound (A), and at least one compound comprising compounds (B) or (C), where: (B) is at least one nitrogen containing organic compound comprising compounds (B1) or (B2); (B1) is a tert-alkanol amine; (B2) is an enaminone or an urea; and (C) is an alkali earth-alumohydroxocarbonate compound (C). Stabilizer system comprises an alkali-earth-double carbonate-chalk compound of formula ((M 1>O) m(M 2>O) n - m(CO 2) o(H 2O) p) (A), and at least one compound comprising compounds (B) or (C), where: (B) is at least one nitrogen containing organic compound comprising compounds (B1) or (B2); (B1) is a tert-alkanol amine; (B2) is an enaminone or an urea; and (C) is an alkali earth-alumohydroxocarbonate compound of formula (((M 1 - xZn x) yAl 2(OH) 4 + 2 yCO 3)(zH 2O)) (C). M 1>, M 2> : different alkali earth metal; m : 0.9-1.1; n : 1.9-2.1 (when p is 0-2.1) or 3.9-4.1 (when p is 0-4.1); o : 0-1.1; M : Mg or Ca; x : 0-0.5; y : 2-8; and z : 0-12. An independent claim is included for a composition comprising a halogen-containing polymer and the system.

Description

The present invention relates to stabilizer systems for halogen-containing polymers and to compositions and articles containing the stabilizer systems and to methods for stabilizing a halogen-containing polymer.

As is known, halogen-containing plastics tend to undergo undesired decomposition and degradation reactions during thermal stress during processing or in long-term use. This problem can be solved by the use of metal-containing stabilizers added to the halogen-containing polymers before or during processing. The known stabilizers include barium-cadmium, lead, organotin and barium-zinc stabilizers. However, all of these stabilizer groups contain heavy metals or contain toxicologically questionable metals, which is disadvantageous in terms of their environmental compatibility.

For these reasons, in recent years increasingly heavy metal-free so-called organic systems have been developed, which are also already being marketed. These are assigned to the solid stabilizers and are traded for reasons of environmental friendliness largely in compacted form. These organically based systems are multi-component mixtures, the main component of which is usually assigned to the substance group of hydrotalcites (magnesium aluminum hydroxycarbonates).

Heavy metal-free hydrotalcite or hydrocalumite (Katoit) compositions with PVC thermostabilizer function are described, for example, in US Pat EP 1 046 668 B1 and EP 0930 332 B1 described.

However, these classes of compounds are relatively expensive and usable only to a limited extent because the naturally occurring forms are either not present in sufficient quantity or contaminated by heavy metal-containing gaits, mainly iron and manganese carbonates. These impurities drastically reduce the stabilizer effect in PVC.

It is therefore necessary to access synthetic methods that allow a wider access to these substance classes. However, the production on an industrial scale is Due to the raw material costs inconvenient. The production is also connected because of the magnesium, calcium and aluminum salts to be used with a considerable wastewater ballast. This fact can not be disregarded in a large-scale synthesis process. Therefore, the search for lower cost substances is still required. Access to them should as far as possible be combined with resource conservation and environmental compatibility.

In recent years, this goal has been partially achieved by chemically modified Dolomite were offered, which are refined by calcination, since Dolomite as such have no stabilizer function. Access to these compounds is based on semi-synthetic methods, as naturally occurring minerals can be used as a starting point. These minerals (dolomites) are available in enormous quantities and often in sufficient purity, so that it is possible to dispense with a further purification associated with wastewater ballasts. The product and performance qualities have been improved by various additives.

Publications can be found in EP-A 0 422 335 and EP-A 0 945 483 , A semi-synthetic production process is in US-A 2006/188428 released.

The previously provided stabilizer combinations containing calcined dolomites, however, are in their majority still heavy metal content or still have too high a heavy metal content or are not fully satisfactory in their performance.

Thus, there is still a need for alternative, inexpensive and highly effective stabilizer systems.

An object of the present invention is thus to provide such stabilizer systems.

• M¹ und M² = verschiedene Erdalkalimetalle;
• m = 0,9 bis 1,1;
• n = 1,9 bis 2,1 und p = 0 bis 2,1 oder 3,9 bis 4,1 und p = 0 bis 4,1;
• o = 0 bis 1,1

und mindestens eine der Verbindungen ausgewählt aus der Gruppe bestehend aus (B) und (C), wobei

• (B) mindestens eine stickstoffhaltige organische Verbindung ausgewählt aus der Gruppe bestehend aus (B1) und (B2) ist, wobei (B1) ein tert. Alkanolamin und (B2) ein Enaminon oder ein Harnstoff ist und
• (C) ein Erdalkali-alumohydroxocarbonat der Formel (C)
  
           (M_1-xZn_x)_yAl₂(OH)_4+2y CO_3*zH₂O     (C)
  
  mit M = Magnesium oder/und Calcium; x = 0 bis 0,5; y = 2 bis 8 und z = 0 bis 12 ist.

The object is achieved by a stabilizer system for halogen-containing polymers comprising an alkaline earth double carbonate lime of the formula (A)

(M ¹ O) _{m *} (M ² O) _{nm *} (CO ₂ ) _{o *} (H ₂ O) _p (A)

With

• M ¹ and M ² = different alkaline earth metals;
• m = 0.9 to 1.1;
• n = 1.9 to 2.1 and p = 0 to 2.1 or 3.9 to 4.1 and p = 0 to 4.1;
• o = 0 to 1.1

and at least one of the compounds selected from the group consisting of (B) and (C), wherein

• (B) at least one nitrogen-containing organic compound selected from the group consisting of (B1) and (B2) , where (B1) is a tert. Alkanolamine and (B2) is an enaminone or a urea and
• (C) an alkaline earth aluminohydroxocarbonate of the formula (C)
  
  (M _1-x Zn _x ) _y Al ₂ (OH) _{4 +} 2yCO _{3 *} zH ₂ O (C)
  
  with M = magnesium or / and calcium; x = 0 to 0.5; y = 2 to 8 and z = 0 to 12.

The systems of the invention serve to stabilize a halogen-containing polymer, with a chlorine-containing polymer, in particular PVC, being preferred.

The alkaline earth double carbonate limestones of formula (A) are preferably dolomite or huntite limestones derived from naturally occurring or synthetic dolomites or huntites, with the naturally occurring material being preferred.

A preferred subject of the present invention is thus a stabilizer system according to the invention, wherein the alkaline earth double carbonate lime (A) is a Huntitbranntkalk of formula (A1)

(CaO) _{m *} (MgO) _{nm *} (CO ₂ ) _o (A1)

with m = 0.9 to 1.1; n = 3.9 to 4.1 and o = 0 to 1.1.

A further preferred subject of the present invention is a stabilizer system according to the invention, wherein the alkaline earth double carbonate lime (A) comprises a dolomitic lime of the formula (A2)

(CaO) _{m *} (MgO) _{nm *} (CO ₂ ) _o (A2)

with m = 0.9 to 1.1; n = 1.9 to 2.1 and o = 0 to 1.1

The extraction is carried out by calcining (firing) at 550 to 1200 ° C. The firing times are preferably 10 to 20 hours. The quicklime can then hydrate by reaction with water to the slaked lime, the deletion can be done partially or wholly. The temperatures for the wet treatment are preferably from 60 to 95 ° C, the reaction times at 40 to 100 hours. The burning can take place in two stages.

Step 1: Whole Calcination to Magnesium Oxide Where Calcium Magnesium Oxide Carbonate of Composition:

MgO _* CaCO ₃ (A4)

(CAS No .: 83897-84-1) is formed. The use of this substance is preferred.

This half-baked dolomite is also known as Magnomasse or Akdolit. This contains a very reactive magnesium oxide ( Ullmann's Encyclopedia of Industrial Chemistry, Verlag Schwarzenberg / Minden-Berlin, 3rd ed. (1960), Vol. 12, p. 125 ).

When extinguishing with water Hydromagnocalcit becomes:

Mg (OH) _{2 *} CaCO ₃

obtained, which can also be used preferably.

Stage 2: partial or total burning to calcium oxide. The use of the substance of the composition resulting from total calcination to calcium-magnesium dioxide (double oxide):

CaMgO ₂ (A3)

(CAS No .: 37247-91-9) is very particularly preferred.

This substance has a metastable crystal lattice, because the resulting calcium oxide and magnesium oxide microcrystals prevent each other from crystal growth due to their regular arrangement ( Ullmann's Encyclopaedia of Ind. Chem., Verlag-Chemie, Weinheim, 5th ed., Vol. 15, p. 611 ).

Depending on the admixtures (gaits) gray or white limestones are obtained. The partial erasure can then take place until the formation of a crumbly mass. The solids are ground at the end of the process to a fine powder which can be coated with fatty acids, preferably palmitic or stearic acid.

Basically, coated compounds are preferred. Their preparation is known in the art. For example, coatings are also used in EP-A 0 422 335 produced.

Another preferred subject of the present application is a stavilizer system according to the invention in which at least one compound (A), (A1), (A2), (A3) and (A4) is present in coated form.

Since the crystal lattice of the Dolomites and Huntites differ from the crystal lattice of calcium (calcium carbonate) and magnesites (magnesium carbonate) in that in the double carbonate dolomite in layers alternately CaO ₆ - and MgO ₆ octahedra with embedded carbonate anions, the structure of lime (CaMgO ₂ ) to calcium oxide (CaO) and magnesium oxide (MgO), both of which crystallize in the common salt lattice. The calcination process thus results in altered structures with alternating calcium oxide and magnesium oxide levels.

The crystal lattice of the Huntite is relatively complicated, since CaO ₆ octahedra and CaO ₆ tetronal prisms are present alongside MgO ₆ octahedra (see Dolomite and Huntite Crystal Structures in: Mineral Structure Data Base, University of Colorado; Dollase WA, Am. Mineral. 71, 163 [1986 ]). Since the lattice sites of the calcium and magnesium ions are retained during firing, the structure of this quicklime is also completely different than with calcium and magnesium oxide.

Another indication of the variation of the crystal lattice arises from the fact that mixtures of calcium and magnesium oxide, which in summary correspond to the dolomite and Huntitbranntkalken, generally have a weaker performance against these. This indicates that calcination processes produce crystal lattices in particularly reactive forms, since larger-volume carbonate anions are replaced by small-volume oxide anions, meaning that there are virtually no vacancies in the crystal lattices. These crystal lattices are due to lattice defects (Defect sites, lattice strains and lattice orientations) higher energy contents associated with metastability, which accounts for the increased activity of the stabilizer components ( Ullmann's Encyclopedia of Industrial Chemistry, Verlag Schwarzenberg / Minden-Berlin, 3rd ed. (1960), Vol. 12, p. 125 ).

Preferred alkaline earth double carbonate lime are dolomite or huntite lime. Particularly preferred is dolomitic lime, with calcium-magnesium dioxide (A3) being very particularly preferred. The concentration range in the halogen-containing polymer is preferably 0.05 to 10 parts by weight per 100 parts by weight of the polymer. Particular preference is given to using from 0.1 to 5 parts by weight.

The components or compounds (B) are characterized by being nitrogenous. In the system according to the invention, one compound or several compounds (B) may be present. The same applies to (A) and (C).

In general, the system according to the invention is characterized in that it contains at least (A) and (B) or (A) and (C) . If more than two, for example three or four compounds of (A), (B), (C) and optionally further compounds are present, it is preferred that (A), (B) and (C) are present.

The component or compound (B1) is preferably at least one trialkanolamine, a bis-alkanol fatty acid amine or a tris-alkanol isocyanurate. One or more of these substances can be used.

mit r = 1 oder 2, R⁶ = C₁ - C₁₂-Alkyl oder CH₂OR⁹; R⁷, R⁸ = unabhängig von einander C₁ - C₂₂-Alkyl, C₃ - C₂₂-Alkenyl und CH₂CHR^6a-OH; R⁹ = C₁ - C₂₀-Alkyl, C₃ - C₁₈-Alkenyl und R¹⁰OCH₂CHR^6aOH-N(R⁷)(R⁸); R^6a = C₁ - C₁₂-Alkyl, R¹⁰ = C₂ - C₁₀-Alkylen oder 1,4-Dimethylol-cyclohexan-diyl, wobei bei r = 1, R⁷ und R⁸ zusammen zusätzlich -(CH₂)₄-, - (CH₂)₅-, -(CH₂)₂O(CH₂)₂-, -(CH₂)₂-N(CH₂CHR⁶-OH)-(CH_2)2- und -CON(CH₂CHR⁶-OH)-CON(CH₂CHR⁶-OH)CO- und bei r = 2, R⁸ außerdem = C₂ - C₁₁-Alkylen, das durch 1 bis 3 N(CH₂CHR⁶-OH)-Gruppen unterbrochen sein kann oder 1,4-Dimethylol-cyclohexan-diyl ist.The component or compound (B1) is particularly preferably tert. Alkanolamines, with tert. Ethanolamines of the formula (B1-a1) are preferred:

with r = 1 or 2, R ⁶ = C ₁ - C ₁₂ alkyl or CH ₂ OR ⁹ ; R ⁷ , R ⁸ = independently of one another C ₁ -C ₂₂ -alkyl, C ₃ -C ₂₂ -alkenyl and CH ₂ CHR ^6a -OH; R ⁹ = C ₁ -C ₂₀ alkyl, C ₃ -C ₁₈ alkenyl and R ¹⁰ OCH ₂ CHR ^6a OH-N (R ⁷ ) (R ⁸ ); R ^6a = C ₁ -C ₁₂ -alkyl, R ¹⁰ = C ₂ -C ₁₀ -alkylene or 1,4-dimethylol-cyclohexanediyl, wherein when r = 1, R ⁷ and R ⁸ together additionally - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₂ O (CH ₂ ) ₂ -, - (CH ₂ ) ₂ -N (CH ₂ CHR ⁶ -OH) - (CH _{2) 2-} and - CON (CH ₂ CHR ⁶ -OH) -CON (CH ₂ CHR ⁶ -OH) CO- and when r = 2, R ⁸ also = C ₂ -C ₁₁ -alkylene, which is substituted by 1 to 3 N (CH ₂ CHR ⁶ -OH) groups or is 1,4-dimethylol-cyclohexanediyl.

C ₁ -C ₂₂ -alkyl is preferred: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl and decyl (with isoforms), undecyl , Dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and docosyl; C ₃ -C ₂₂ alkenyl: preferably allyl and oleyl; C ₂ -C ₁₁ -alkylene: preferably ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, hexylene, octylene, decylene and undecylene.

Preferred compounds of formula (B1-A1), trialkanolamines such as triethanolamine and Trisalkanolisocyanurate (reaction products of cyanuric acid with alkene oxides), and bis-alkanolfettsäureamine (especially with fatty acid = C ₁₂ - C ₁₈ - carboxylic acid or oil or linoleic acid and alkanol = ethanol , Isopropanol and isobutanol), with oleyldiethanolamine, oleyldiisopropanolamine and stearyldiethanolamine, as well as reaction products of monoglycidyl and diglycidyl ethers with diethanol and diisopropanolamine, and triethyl or triisopropyl isocyanurate being most preferred.

Particularly preferred are triethanolamine, oleyldiethanolamine and trishydroxyethyl isocyanurate (THEIC).

The component or compound (B2) is preferably at least one substituted aminouracil, an aminocrotonic acid ester or a substituted urea. One or more of these substances can be used.

The enaminones (B2-a) all have the structural element R ⁴ NH - C = CH - CO -.

These include the enaminoesters (B2-a1) (aminocroton esters) and the aminopyrimidinones (B2-a2) and (B2-a3) (aminouracils), these being preferably described by the following structures:

worin
R¹ = unverzweigtes oder verzweigtes C₂ - C₂₀ -Alkylen, das durch 1 bis 4 O - oder S- Atome unterbrochen oder/und durch 1 bis 4 OH-Gruppen substituiert sein kann, oder 1,4-Dimethylol-cyclohexan-diyl, Polyethylen( oder -propylen)glykol-a, ω-diyl (vorzugsweise ist Poly = Tetra bis Deka), Polyglyceryl -α,ω-diyl (vorzugsweise ist Poly = Tetra bis Deka) oder Glycerin-triyl, Trimethylolethan(oder -propan)-triyl, Pentaerythrit-tri(oder -tetra)yl, Bistrimethylolethan(oder -propan)-tri(oder -tetra)yl, Diglycerin-tri(oder tetra)yl, Tetrit-tetrayl, Triglycerin-tri(oder -tetra, -penta)yl, Pentit-pentayl, Dipentaerythrit-penta(oder -hexa)yl und Hexit-hexayl; und q = 2-6.
R² = C₁ - C₂₀-Alkyl, C₃ - C₆-Alkenyl, C₇ - C₉-Phenylalkyl, unsubstituiertes oder mit 1 bis 3 C₁ - C₄-Alkyl-, C₁- C₄-Alkoxy- oder Hydroxygruppen substituiertes Phenyl
R³ = R¹ oder Wasserstoff.
R⁴ = Wasserstoff, Hydroxy-C₂ - C₄-Alkyl, Hydroxyphenyl, C₁ - C₄-Alkoxyphenyl
R⁵ = C₁ - C₂₀-AlkylThe substituted ureas (B2-b) include the phenylureas (B2-b1) and (B2-b2) as well as the cyanoacetylureas (B2-b3) which can be described by the following structural formulas:

wherein
R ¹ = unbranched or branched C ₂ -C ₂₀ -alkylene, which may be interrupted by 1 to 4 O or S atoms and / or substituted by 1 to 4 OH groups, or 1,4-dimethylol-cyclohexanediyl , Polyethylene (or -propylene) glycol-a, ω-diyl (preferably poly = tetra to deca), polyglyceryl-α, ω-diyl (preferably poly = tetra to deca) or glycerol-triyl, trimethylolethane (or -propane) ) triyl, pentaerythritol tri (or tetra) yl, bistrimethylolethane (or propane) tri (or tetra) yl, diglycerol tri (or tetra) yl, tetrit tetrayl, triglycerol tri (or tetra, -penta) yl, pentit-pentyl, dipentaerythritol-penta (or -hexa) yl and hexitol-hexyl; and q = 2-6.
R ² = C ₁ -C ₂₀ -alkyl, C ₃ -C ₆ -alkenyl, C ₇ -C ₉ -phenylalkyl, unsubstituted or with 1 to 3 C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or hydroxy-substituted phenyl
R ³ = R ¹ or hydrogen.
R ⁴ = hydrogen, hydroxy-C ₂ - C ₄ -alkyl, hydroxyphenyl, C ₁ - C ₄ -alkoxyphenyl
R ⁵ = C ₁ -C ₂₀ -alkyl

It is preferred that: C ₃ - C ₆ alkenyl: allyl, butenyl and hexenyl; C ₇ -C ₉ -phenylalkyl: Benzyl and phenethyl; by hydroxy groups subst. Phenyl: o- and p-hydroxyphenyl; C ₁ -C ₄ alkoxy: methoxy and ethoxy; by C ₁ - C ₄ -alkoxy Subst. Phenyl: o-methoxy and p-methoxyphenyl. For further definitions see (B1).

The classes of compounds (B2-a2) and (B2-a3) are partly commercially available or their synthesis is described in more detail in EP 0768 336 . EP 1 510 545 . EP 0 967 209 . EP 0 967 208 . EP 0 962 491 and EP 1 044 968 , Representatives of the structures (B2-a1) are commercially available or, as in EP 433 230 described, produced. Products of formula (B2-b3) are also commercially available. Their synthesis is exemplary in EP 0 962 491 published.

Preferred compounds of the formula (B2-a1) are bis-1,4-butanediyl-3-aminocrotonate or bis-thiodiethandiyl-3-aminocrotonate.

Preferred aminouracils of the formulas (B2-a2) and (B2-a3) are 6-amino-1,3-dimethyluracil, 6-amino-1-octyluracil, 6-amino-1,3-dibenzyluracil, 6- (2-hydroxyanilino ) -1,3-dimethyluracil, 6- (2-methoxyanilino) -1,3-dimethyluracil, 5,5'-heptylidene-bis-6-amino-1,3-dimethyluracil, 5,5'-octylidene bis- 6-amino-1,3-dimethyluracil and 5,5'-dodecylidene-bis-6-amino-1,3-dimethyluracil. Particularly preferred are 6-amino-1,3-dimethyluracil and 5,5'-dodecylidene-bis-6-amino-1,3-dimethyluracil.

Preferred ureas of the formula (B2-b3) are cyanoacetyl-1,3-dialkyl (dibenzyl) ureas, of which cyanoacetyl-1,3-dimethylurea is particularly preferred.

The concentration range for the components (B1) and (B2) is preferably 0.05 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, more preferably 0.3 to 3 parts by weight of Compound based on 100 parts by weight of halogen-containing polymer.

The component or compound (C) is assigned to the alkaline earth metal hydroxocarbonates, which can be described by the formula:

(M _1-x Zn _x ) _y Al ₂ (OH) _{4 +} 2yCO _{3 *} zH ₂ O (C)

with M = magnesium or / and calcium; x = 0 to 0.5; y = 2 to 8 and z = 0 to 12.

The main representatives are the substance classes of hydrotalcites (Mg / Al and Mg / Zn / Al-containing) and calcium carbonated hydroxodialuminates (Ca / Al-containing).

The component or compound (C) is preferably at least one magnesium or a magnesium zinc alumohydroxocarbonate (C1) or a calcium carbonate hydroxodialuminate (C2). One or more of these substances can be used.

hydrotalcites

The chemical composition of these compounds is known to the person skilled in the art, for example from the documents PS - DE 38.43.581 A1 . US 4,000,100 . EP 0,062,813 A1 and WO 93/20135 and PS- DE 102.17.364 A1 (Süd-Chemie). They have the following composition:

(Mg _1-x Zn _x ) _y Al ₂ (OH) _{4 +} 2yCO _{3 *} zH ₂ O (C1)

with x = 0 to 0.5; y = 2 to 8 and z = 0 to 12.

• Al₂O₃ * 6MgO * CO₂ * 12 H₂O, Mg_4,5Al₂(OH)₁₃ * CO₃ * 3,5 H₂O, 4MgO * Al₂O₃ * CO₂ * 9 H₂O, 4MgO * Al₂O₃ * CO₂ * 6 H₂O, ZnO * 3MgO * Al₂O₃ * CO₂ * 8-9 H₂O und
• ZnO * 3MgO * Al₂O₃ * CO₂ * 5-6 H₂O

Examples for this are:

• Al ₂ O ₃ * 6MgO * CO ₂ * 12H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ * CO ₃ * 3.5H ₂ O, 4MgO * Al ₂ O ₃ * CO ₂ * 9H ₂ O , 4MgO * Al ₂ O ₃ * CO ₂ * 6H ₂ O, ZnO * 3MgO * Al ₂ O ₃ * CO ₂ * 8-9 H ₂ O and
• ZnO * 3MgO * Al ₂ O ₃ * CO ₂ * 5-6H ₂ O

Particularly preferred are the types Alcamizer 1 and 2, Alcamizer P 93-2 (Alcamizer 4) (manufacturer Kyowa Chemical Ind. Co., JP) and Sorbacid 911 (manufacturer SÜD-CHEMIE, DE). Very particular preference is given to using dehydrated hydrotalcites.

Calcium Carbonato hydroxodialuminates

Calcium carbonated hydroxodialuminates (CAHC) are new synthetic minerals that exhibit costabilizer function in PVC (ADDCON 2007 3 / 6.09.2007, Frankfurt / M). They can be described by the following idealized formula:

Ca ₄ Al ₂ (OH) ₁₂ CO _{3 *} zH ₂ O (C2)

By adding calcium-magnesium-dioxide a synergistic increase in performance is possible as well as hydrotalcites. Manufacturer and supplier is the company NABALTEC AG, DE. The product is sold under the name ACTILOX CAHC.

Compounds (C) may be contained in the polymer at 0.005 to 9 parts by weight per 100 parts by weight of polymer. Preference is given to 0.05 to 5 parts by weight, very particularly preferably 0.5 to 3 parts by weight.

• (A3 oder A4) + (B1-a2), (A3 oder A4) + (B1-a3) und (A3 oder A4) + (B1-b3) (A3 oder A4) + (B1-a2) + (C1), (A3 oder A4) + (B1-a3) + (C1) und (A3 oder A4) + (B1-b3) + (C1), (A3 oder A4) + (B1-b3) + (C2), (A3 oder A4) + (B1-a3) + (C1)

sowie (A3 oder A4) + (C1) und (A3 oder A4) + (C2), die zusätzlich Trishydroxyethylisocyanurat (THEIC) enthalten.Particularly preferred are the following combinations:

• (A3 or A4) + (B1-a2), (A3 or A4) + (B1-a3) and (A3 or A4) + (B1-b3) (A3 or A4) + (B1-a2) + (C1) , (A3 or A4) + (B1-a3) + (C1) and (A3 or A4) + (B1-b3) + (C1), (A3 or A4) + (B1-b3) + (C2), ( A3 or A4) + (B1-a3) + (C1)

and (A3 or A4) + (C1) and (A3 or A4) + (C2), which additionally contain trishydroxyethyl isocyanurate (THEIC).

Very particular preference is given to the combinations (A3 or A4) + trialkanolamine or trishydroxyethyl isocyanurate.

• Zeolithe, Dawsonite und Schichtgitterverbindungen
• Catena-µ-2,2',2"-nitrilotrisethanol-perchlorato (-triflato)-Natrium- oder Lithium-Innerkomplexe bzw. Lithium- oder Natriumperchlorate (-triflate) in gelöster bzw. geträgerter Form
• Fettsaure Calcium- oder Zinksalze (Calcium- oder Zinkseifen)
• Polyole und Zuckeralkohole und/oder 1,4-Dihydropyridin-Derivate (DHP)
• Lineare oder cyclische β-Diketone bzw. β-Ketoester und deren Calcium-, Magnesium-oder Zinksalze
• Phosphorigsäureester (Phosphite) und sterisch gehinderte Amine
• Glycidylverbindungen und epoxidierte Fettsäurester
• Antioxidantien, UV-Absorber und optische Aufheller
• Pigmente und Biozide
• Füllstoffe und Treibmittel
• Gleitmittel und Weichmacher
• Flammschutzmittel und Rauchverminderer

Optionally, the stabilizer system according to the invention may also contain further additives, such as:

• Zeolites, dawsonites and layered lattice compounds
• Catena μ-2,2 ', 2 "nitrilotrisethanol perchlorato (triflato) sodium or lithium inner complexes or lithium or sodium perchlorates (triflates) in dissolved or supported form
• Fatty acid calcium or zinc salts (calcium or zinc soaps)
• Polyols and sugar alcohols and / or 1,4-dihydropyridine derivatives (DHP)
• Linear or cyclic β-diketones or β-ketoesters and their calcium, magnesium or zinc salts
• Phosphorous acid esters (phosphites) and sterically hindered amines
• Glycidyl compounds and epoxidized fatty acid esters
• Antioxidants, UV absorbers and optical brighteners
• Pigments and biocides
• Fillers and blowing agents
• Lubricants and plasticizers
• Flame retardants and smoke reducers

zeolites

They can be described by the formula M _{x / n} [(AlO ₂ ) _x (SiO ₂ ) _y ] _* w H ₂ O, where n is the charge of the cation M; M is an element of the first or second main group, such as Li, Na, K or NH _4, and Mg, Ca, Sr or Ba; y: x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and w is a number from 0 to 300, preferably from 0.5 to 30.

Examples of zeolites are sodium aluminosilicates of the formulas
Na ₁₂ Al ₁₂ Si ₁₂ O _{48 *} 27 H ₂ O [zeolite A], Na ₆ Al ₆ Si ₆ O _{24 *} 2 NaX _* 7.5 H ₂ O, X = OH, halogen, ClO ₄ [sodalite]; Na ₆ Al ₆ Si ₃₀ O _{72 *} 24 H ₂ O; Na ₈ Al ₈ Si ₄₀ O _{96 *} 24 H ₂ O; Na ₁₆ Al ₁₆ Si ₂₄ O _{80 *} 16 H ₂ O; Na ₁₆ Al ₁₆ Si ₃₂ O _{96 *} 16 H ₂ O; Na ₅₆ Al ₅₆ Si ₁₃₆ O _{384 *} 250 H ₂ O [zeolite Y], N a ₈₆ Al ₈₆ Si ₁₀₆ O _{384 *} 264 H ₂ O [zeolite X]; Na ₂ O, Al ₂ O ₃ , (2-5) SiO ₂ , (3,5-10) H ₂ O [zeolite P]; Na ₂ O, Al ₂ O ₃ , 2SiO _2, * (3,5-10) H ₂ O (zeolite MAP); or the zeolites which can be prepared by partial or complete replacement of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na, K) ₁₀ Al ₁₀ Si ₂₂ O _{64 *} 20 H ₂ O; Ca _4.5 Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] _* 30 H ₂ O; K ₉ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] _* 27 H ₂ O. Very particular preference is given to Na zeolite A and Na zeolite MAP (see also PS. US 6,531,533 ). Likewise preferred are zeolites with extremely small particle size, in particular of the Na A and Na P type, as they are also known in PS. US 6,096,820 are described.

Layer lattice compounds

These include Titania hydrotalcites (Al / Mg / Ti / carbonate-containing), lithium hydrotalcites (Li / Al / carbonate or Li / Mg / Al / carbonate-based) and calcium aluminum hydroxo-hydrogen phosphites as described in PS DE 44.25266 A1 (Metal Company), PS EP 0,549,340 A1 (Mizusawa Ind. Chem.) And PS - JP 0.761.756 A1 (Fuji Chem. Ind.). You can by the following general formula:

M ₂ ⁺ _1-x M ₃ ⁺ _x (OH) ₂ (A ⁿ ) _{x / b} * d H ₂ O

be described, wherein
M ²⁺ = as cation one or more of the metals from the group Mg, Ca, Sr,
Zn or Sn, M ³⁺ = as cation A1 or B, A ^{n represents} an anion with the valence -n,
b = n is a number of 1-2, 0 <x <0.5, d is a number from 0-20. Preference is given to compounds with
A ⁿ = OH ^-, ClO ₄ ^-, HCO ₃ ^-, CH ₃ COO ^-, C ₆ H ₅ COO ^-, CO ₃ ^2-, (CHOHCOO) ₂ ^2-, (CH ₂ C00) ₂ ^2-, CH ₃ CHOHCOO ^- , HPO ₃ ^- or HPO ₄ ^2- .

Titania hydrotalcites

Titanium-containing hydrotalcites are in PS - WO 95/21127 described. Compounds of this type having the general formula Al _a Mg _b Ti _c (OH) _d (CO ₃ ) _e * m H ₂ O, where a: b = 1: 1 to 1:10; 2≤b≤10; 0 <c <5; 0 ≤m <5, and d and e are chosen to give a basic, charge-free molecule can also be used.

Lithium hydrotalcites

Lithium aluminum layer lattice compounds have the general formula:

Li _a M ^II _(b-2a) Al _{(2 + a)} OH _{(4 + 2b) (} A ^n- ) _{(2 / n) *} m H ₂ O

wherein
M ^II Mg, Ca or Zn and
A ^{n is} a selected anion of valence n or a mixture of anions and the indices are in the range of
0 <a <(b-2) / 2,
1 <b <6 and
m = 0 to 30
are with the restriction that (b-2a)> 2 or
the general formula:

[Al ₂ (Li _(1-x) .M ^II _x ) (OH) ₆ ] _n (A ^n- ) _{(1 + x)} * m H ₂ O

wherein
M ^II , A, m and n have the above meaning and
x the condition satisfies 0.01 ≤ x <1

The preparation of said layer lattice compounds is characterized in that lithium hydroxide, oxide and / or its compounds convertible into hydroxide, metal (II) hydroxides, oxides and / or their hydroxides convertible compounds of said metals and aluminum hydroxides in the aqueous medium and / or their compounds convertible into hydroxides and acids and / or their salts or mixtures thereof at a pH of 8 to 10 and at temperatures of 20 to 250 ° C with each other and the resulting solid reaction product separated.

The reaction time is preferably 0.5 to 40 hours, especially 3 to 15 hours.
The reaction product directly obtained from the reaction described above can be separated from the aqueous reaction medium by known methods, preferably by filtration. The workup of the separated reaction product is also carried out in a conventional manner, for example by washing the filter cake with water and drying the washed residue at temperatures of for example 60 to 150 ° C, preferably at 90 to 120 ° C.

For the reaction with aluminum, finely divided, active metal (III) hydroxide in combination with sodium hydroxide, as well as a NaAlO ₂ can be used. Lithium or one of the stated metal (II) compounds can be used in the form of finely divided lithium oxide or hydroxide or mixtures thereof or of finely divided metal (II) oxide or hydroxide or mixtures thereof. The corresponding acid anions can be used in differently concentrated form, for example directly as acid or else as salt.

The reaction temperatures are preferably between about 20 and 250 ° C, more particularly between about 60 and 180 ° C. Catalysts or accelerators are not required. The substances can be removed as water of crystallization completely or partially by treatment. When used as stabilizers, the dried layer lattice compounds do not split off water or another gas at the processing temperatures of 160 to 220 ° C. which are usual for PVC, so that no disturbing bubble formation occurs in the molded parts.

The anion A ⁿ in the above general formula may include sulfate, sulfite, sulfide, thiosulfate, peroxosulfate, peroxodisulfate, hydrogenphosphate, hydrogenphosphite, carbonate, halides, nitrate, nitrite, hydrogensulfate, bicarbonate, hydrogensulfite, hydrogensulfide, dihydrogenphosphate, dihydrogenphosphite, monocarboxylic anions such as acetate and Benzoate, amide, azide, hydroxide, hydroxylamine, hydroazide, acetylacetonate, phenolate, pseudohalides, halogenites, halogenates, perhalates, I ₃ ^- , permanganate, dianions of dicarboxylic acids such as phthalate, oxalate, maleate or fumarate, bisphenolates, phosphate, pyrophosphate, phosphite, Pyrophosphite trianions of tricarboxylic acids such as citrate, trisphenolates and more, as well as mixtures thereof. Among them, hydroxide, carbonate, phosphite and maleate are preferable. To improve the dispersibility of the substances in halogen-containing thermoplastic polymer compositions, the same may be surface-treated with a higher fatty acid, eg stearic acid, an anionic surface-active agent, a silane coupler, a titanate coupler or a glycerin fatty acid ester.

Calcium aluminum hydroxo hydrogen phosphites

und m = 0 - 12 bedeuten, ausgenommen y = 1, wenn x = 2 - 8 ist,For the novel stabilizer combinations suitable compounds from the group of basic calcium-aluminum-hydroxy-hydrogen phosphites of the general formula

Ca _x Al ₂ (OH) _{2 (x + 2)} HPO _{3 *} H ₂ O,

where x = 2 - 8 and

Ca _x Al ₂ (OH) _{2 (x + 3-y)} (HPO ₃ ) _{y *} m H ₂ O,

where x = 2 - 12, $$\frac{\mathrm{2}\mathrm{x}\mathrm{+}\mathrm{5}}{\mathrm{2}}\mathrm{>}\mathrm{y}\mathrm{>}\mathrm{0}$$

and m = 0-12, except y = 1, when x = 2-8,

can be prepared, for example, by a process in which mixtures of calcium hydroxide and / or calcium oxide, aluminum hydroxide and sodium oxide or of calcium hydroxide and / or calcium oxide and sodium aluminate with phosphorous acid in corresponding amounts to produce the desired calcium aluminum hydroxyhydrogen phosphites in aqueous Reacting medium and the reaction product separated in a conventional manner and win. The reaction product directly obtained from the reaction described above can be separated from the aqueous reaction medium by known methods, preferably, for example by washing the filter cake with water and drying the washed residue at temperatures of for example 60-130 ° C, preferably 90-120 ° C.

For the reaction, both finely divided, active aluminum hydroxide in combination with sodium hydroxide and a sodium aluminate can be used. Calcium may be used in the form of finely divided calcium oxide or calcium hydroxide or mixtures thereof. The phosphorous acid can be used in different concentrated form. The reaction temperatures are preferably between 50 and 100 ° C, more preferably between about 60 and 85 ° C. Catalysts or accelerators are not required, but do not bother. In the compounds, the water of crystallization can be completely or partially removed by thermal treatment.

When used as stabilizers, the dried calcium-aluminum-hydroxy phosphites do not split off water at the processing temperatures of 160-200 ° C., which are customary, for example, for hard PVC, so that no disturbing bubble formation occurs in the molded parts.

To improve their dispersibility in halogen-containing thermoplastic resins, the compounds can be coated in a known manner with surfactants. The class of compounds, also called CHAP or CAP compounds, is described in EP 0.506.831A1

The above-described calcium-aluminum hydroxo-hydrogen phosphites and titanium-containing hydrotalcites may be crystalline and also partially crystalline and / or amorphous.

Dawsonite (Alkalialumocarbonate)

These are given by the general formula

M [Al (OH) ₂ CO ₃ ] (M = Na, K)

described. The preparation of Na-Dawsonite (DASC or SAC) and K-Dawsonite (DAPC or PAC) is published in PS - US 3,501,264 and US 4,221,771 as well as in PS EP 0394.670 A1 , The synthesis can be carried out hydrothermally or non-hydrothermally. The products may be crystalline or amorphous. Also included in the substance class are sodium magnesium alumino carbonates (SMAC); their preparation is described PS- US 455,055,284 ,

Calcium aluminum hydroxo-hydrogen phosphites and / or zeolites and / or dawsonites and / or layered lattice compounds can be used in amounts of, for example, 0.1 to 20, advantageously 0.1 to 10 and in particular 0.1 to 5 parts by weight, based on 100 parts by weight of halogen-containing polymer.

Catena μ - 2,2 ', 2 "nitrilotrisethanol perchlorato (triflato) sodium or lithium

wobei

• Mt = Li oder Na
• An = OClO₃ oder OS(O₂)CF₃

These four inner complexes are coordination polymers with the following monomer unit:

in which

• Mt = Li or Na
• An = OClO ₃ or OS (O ₂ ) CF ₃

An = OClO ₃ is preferred, with Mt = Na (TEAP) being particularly preferred. Their use as stabilizers is described in WO 2006/136191 , Very particular preference is given to a phlegmatization of concentrated aqueous TEAP solutions on PVC. This production process is described in the German patent application with the application number DE 10 2007 050 428.6 described.

Sodium (lithium) perchlorate (triflate) in dissolved or supported form

These lithium or sodium salts can be used as solutions, with the following solvents being preferred: water, glycols, glycol ethers, (poly) glycerols and polyglycol ethers.

• Siliciumdioxid (Kieselgur), Calciumsilikat, Calciumcarbonat, Calciumoxid, Calciumhydroxid, Na-Zeolith A, Hydrotalcit und calcinierter Dolomit, wobei letzerer bevorzugt ist.

However, particular preference is given to supported formulations of the salts, wherein the salt is sorbed in dissolved form (usually aqueous) on a solid support in a homogeneous distribution from (ad). The following substances are to be mentioned:

• Silica (diatomaceous earth), calcium silicate, calcium carbonate, calcium oxide, calcium hydroxide, Na zeolite A, hydrotalcite and calcined dolomite, the latter being preferred.

These sodium or lithium compounds show in PVC, preferably in zinc-free formulations, a booster effect. They are preferably useful in the substrate of 0.001 to 5 phr, preferably from 0.01 to 3 phr, and most preferably from 0.01 to 2 phr used.

The compounds of this category are preferably combined with systems free of zinc carboxylates but containing (B1) or / and (B2) .

metal soaps

Calcium soaps are primarily calcium carboxylates, preferably longer chain carboxylic acids. Common examples are stearates and laurates, including oleates and salts of short-chain aliphatic or aromatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, sorbic acid; Oxalic, malonic, succinic, glutaric, adipic, fumaric, citric, benzoic, salicylic, phthalic, hemimellitic, trimellitic, pyromellitic, and also overbased calcium carboxylates.

Preference is given to calcium laurate, calcium stearate, calcium behenate, calcium versatate and calcium abietate.

zinc soaps

The zinc soaps are primarily zinc carboxylates. These are compounds from the series of aliphatic saturated and unsaturated C _1-22 carboxylates, aliphatic saturated or unsaturated C _2-22 carboxylates which are substituted with at least one OH group or the chain of which at least by one or more O atoms, is interrupted (oxa acids), of the cyclic and bicyclic carboxylates having 5-22 C atoms, which is unsubstituted, with at least one OH-group-substituted and / or C _1-16 alkyl-substituted phenyl carboxylates, phenyl-C _{of: 1} - ₁₆ alkylcarboxylates, or optionally substituted by C ₁ - ₁₂ alkyl-substituted phenolates, or abietic acid. Zn-S compounds are, for example, Zn-mercaptides, Zn-mercaptocarboxylates and Zn-mercaptocarboxylic acid esters.

Specifically, as examples, the zinc salts of monovalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, enanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, palmitic acid , Lauric, isostearic, stearic, 12-hydroxystearic, 9,10-dihydroxystearic, oleic, ricinoleic, 3,6-dioxaheptanoic, 3,6,9-trioxadecanoic, behenic, benzoic, p-tert-butylbenzoic, dimethylhydroxybenzoic, 3.5 -Di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, Salicylic acid, p-tert-octylsalicylic acid, and sorbic acid, cinnamic acid, mandelic acid, glycolic acid; Zinc salts of divalent carboxylic acids or their monoesters, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, pentane-1,5-dicarboxylic acid, hexane-1,6-dicarboxylic acid, heptane-1, 7-dicarboxylic acid, octane-1, 8-dicarboxylic acid, 3,6,9-trioxadecane-1,10-dicarboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid, malic acid, salicylic acid, polyglycol dicarboxylic acid (n = 10-12), phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and the di- or tri-esters of tri- or tetravalent carboxylic acids, such as hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid and also so-called overbased zinc carboxylates or zinc lauryl mercaptide, zinc thioglycolate, zinc thiosalicylate, zinc bis-i-octyl thioglycolate, zinc mercaptopropionate, zinc thiolactate, zinc thiomalate , Zinc bis-octylmercaptopropionate, zinc bis-isooctylthiolactate and zinc bislauryl thiomalate.

In addition, inorganic zinc compounds such as zinc oxide, zinc hydroxide, zinc carbonate or basic zinc carbonate can be used.

Preference is given to neutral or basic zinc carboxylates of a carboxylic acid having 1 to 22 C atoms (zinc soaps), such as, for example, benzoates or alkanoates, preferably C ₈ -alkanoates, stearate, oleate, laurate, palmitate, behenate, versatate, hydroxystearates and -oleates, dihydroxystearates, p-tert-butylbenzoate, or (iso) octanoate. Particularly preferred are stearate, laurate, oleate, versatate, behenate, benzoate, p-tert-butylbenzoate, 2-ethylhexanoate and abietate.

The metal soaps or mixtures thereof can be used in an amount of, for example, 0.001 to 10 parts by weight, advantageously 0.01 to 8 parts by weight, particularly preferably 0.05 to 5 parts by weight, based on 100 parts by weight PVC, are applied.

Polyols and sugar alcohols

Suitable compounds of this type are, for example: pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimethylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lycasin, mannitol, lactose, leucrose, disaccharide alcohols such as lactitol, maltitol and palatinite. Tetramethylcyclohexanol, tetramethylolcyclopentanol, tetramethylolpyranol, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1-O-α-D-glycopyranosyl-D-mannitol dihydrate. Preference is given to disaccharide alcohols. Also used are polyol syrups such as sorbitol, mannitol and maltitol syrups.

Dihydropyridine derivatives (DHP)

oder Poly-1,4-Dihydropyridin ^*
* = Die Struktur der subst. Poly-1,4-Dihydropyridine wird beschrieben in W02006/0136191 .
worin
R³ = C₁- C₂₀-Alkyl, C₃ - C₆-Alkenyl, C₇ - C₉-Phenylalkyl, unsubstituiertes oder mit 1 bis 3 C₁ - C₄-Alkyl-, C₁- C₄-Alkoxy- oder Hydroxygruppen substituiertes Phenyl ist.These are described by the following general formula:

or poly-1,4-dihydropyridine ^*
* = The structure of the subst. Poly-1,4-dihydropyridine is described in W02006 / 0136191 ,
wherein
R ³ = C ₁ -C ₂₀ -alkyl, C ₃ -C ₆ -alkenyl, C ₇ -C ₉ -phenylalkyl, unsubstituted or with 1 to 3 C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or hydroxy-substituted phenyl.

The polyols and dihydropyridines may be used in an amount of, for example, from 0.01 to 20, suitably from 0.1 to 20 and especially from 0.1 to 10 parts by weight, based on 100 parts by weight of PVC.

Linear or cyclic β- diketones and β - ketoesters and their metal salts

Useful 1,3-dicarbonyl compounds are linear or cyclic dicarbonyl compounds. Preferably, dicarbonyl compounds of the formula R ' ₁ CO CHR ₂ ^' -COR ' ₃ are used, wherein R' ₁ C ₁ -C ₂₂ alkyl, C ₅ -C ₁₀ hydroxyalkyl, C ₂ -C ₁₈ alkenyl, phenyl, by OH , C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen substituted phenyl, C ₇ -C ₁₀ phenylalkyl, C ₅ -C ₁₂ cycloalkyl, C ₁ -C ₄ alkyl-substituted C ₅ -C ₁₂ cycloalkyl or a group -R ₅ -S-R _'6 or R' ₅ -O-R _'6; R ' _{2 is} hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₁₂ alkenyl, phenyl, C ₇ -C ₁₂ alkylphenyl, C ₇ -C ₁₀ phenylalkyl or a group -CO-R'₄; R _'3 is a for R' has the meanings given ₁ or C ₁ -C ₁₈ alkoxy, R _{'4 is} C ₁ -C ₄ alkyl or phenyl; R ' _{5 is} C ₁ -C ₁₀ -alkylene and R' _{6 is} C ₁ -C ₁₂ -alkyl, phenyl, C ₇ -C ₁₈ -alkylphenyl or C ₇ -C ₁₀ -phenylalkyl.

These include the hydroxyl-containing diketones PS - EP 0 346 279 A1 and the oxa- and thia-diketones in PS - EP 0307,358 A1 as well as the isocyanuric acid based ketoester in PS - US 4,339,383 (THEIC-ester).

R ' ₁ and R' ₃ as alkyl may be in particular C ₁ -C ₁₈ -alkyl, for. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl. R ' ₁ and R' ₃ as hydroxyalkyl are in particular a group - (CH ₂ ) _n -OH, where n is 5, 6 or 7.

R ' ₁ and E' ₂ as alkenyl may be, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.

R ' ₁ and R' ₃ as phenyl substituted by OH, alkyl, alkoxy or halogen may, for example, be tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl.

R ' ₁ and R' ₃ as phenylalkyl are in particular benzyl. R ' ₂ and R' ₃ as cycloalkyl or alkylcycloalkyl are in particular cyclohexyl or methylcyclohexyl.

R ' ₂ as alkyl may in particular be C ₁ -C ₄ -alkyl. R ' ₂ as C ₂ -C ₁₂ alkenyl may in particular be allyl. R ' ₂ as alkylphenyl may in particular be tolyl. R ' ₂ as phenylalkyl may be in particular benzyl. Preferably, R ' _{2 is} hydrogen. R ' ₃ as the alkoxy may be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy. R ' ₅ as C ₁ -C ₁₀ -alkylene is in particular C ₂ -C ₄ -alkylene. R ' ₆ as alkyl is in particular C ₄ -C ₁₂ alkyl, z. For example, butyl, hexyl, octyl, decyl or dodecyl.

R ' ₆ as alkylphenyl is in particular tolyl. R ' ₆ as phenylalkyl is in particular benzyl.

Examples of 1,3-dicarbonyl compounds of the above general formula and their alkali, alkaline earth and zinc chelates are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthioheptanedione-2,4, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, Palmitoylbenzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, 5-hydroxycapronylbenzoylmethane, tribenzoylmethane, bis (4-methylbenzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoylbenzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl- 1-acetylnonane, benzoyl-acetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoylformylmethane, benzoyl-phenylacetylmethane, biscyclohexanoyl-methane, di-pivaloyl-methane, 2-acetyl-cyclo-pentanone, 2- Benzoylcyclopentanone, methyl, ethyl and di-acetoacetate, methyl and ethyl benzoyl, propionyl and butyryl acetoacetate, triacetylmethane, acetoacetic methane yl, ethyl, hexyl, octyl, dodecyl or octadecyl ester, benzoyl acetic acid, methyl, ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl ester, and propionyl and butyrylacetic acid C ₁ -C ₁₈ alkyl esters. Stearoylacetic acid ethyl, propyl, butyl, hexyl or octyl esters and polynuclear β-ketoesters as in PS EP-A 0 433 230 described and dehydroacetic acid and their zinc, magnesium or alkaline earth metal salts. Preferred are Ca, Mg and Zn salts of acetylacetone and dehydroacetic acid.
Especially preferred are 1,3-diketo compounds of the above formula wherein R _{'1 is} C ₁ -C ₁₈ alkyl, phenyl, substituted by OH, methyl or methoxy, C ₇ -C ₁₀ phenylalkyl or cyclohexyl, R ' _{2 is} hydrogen and R' _{3 has} one of the meanings given for R ' ₁ . Also included are heterocyclic 2,4-diones such as N-phenyl-3-acetylpyrrolidine-2,4-dione. Other representatives of this category are described in PS - EP 0,734,414 A1 , The 1,3-diketo compounds may be used in an amount of, for example, 0.01 to 10, preferably 0.01 to 3, and especially 0.01 to 2, parts by weight based on 100 parts by weight of PVC.

Phosphorous acid ester (phosphites)

Examples of these are trioctyl, tridecyl, tridodezyl, tritridezyl, tripentadezyl, trioleyl, tristearyl, triphenyl, trilauryl, tricresyl, tris-nonylphenyl, tris-2,4-t-butyl-phenyl or Trizyklohexylphosphit. Other suitable phosphites are mixed aryldialkyl or alkyl diaryl phosphites such as phenyldioctyl, phenyldidezyl, phenyldidodezyl, phenylditridezyl, phenylditetradezyl, phenyldipentadecyl, octyldiphenyl, decyldi-phenyl, undecyldiphenyl, dodecyldiphenyl, tridecyldiphenyl, tetradecyldiphenyl , Pentadezyldiphenyl-, Oleyldiphenyl-, Stearyldiphenyl- and Dodezyl-bis-2,4-di-t-butyl-phenyl phosphite. Furthermore, it is also possible to use phosphites of various diols or polyols, for example tetraphenyldipropylene glycol diphosphite, poly (dipropylene glycol) phenyl phosphite, tetraisodecyl dipropylene glycol diphosphite, tris-dipropylene glycol phosphite, tetramethylolcyclohexanol decyl diphosphite, tetramethylolcyclohexanol butoxyethoxyethyl diphosphite, tetramethylolcyclohexanol nonylphenyl diphosphite, bisnonylphenyl di-trimethylolpropane diphosphite, bis-2-butoxyethyl-di-trimethylolpropane diphosphite, trishydroxyethylisocyanurate hexadecyltriphosphite, didezylpentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis-2,4-di-t-butylphenyl pentaerythritol diphosphite, and mixtures of these phosphites and aryl / alkyl phosphite mixtures of random composition (H ₁₉ C ₉ -C ₆ H ₄ ) O _1.5 P (OC _12.13 H _25.27 ) _1.5 or (C ₈ H ₁₇ -C ₆ H ₄ -O-) ₂ P (iC ₈ H ₁₇ O), (H ₁₉ C ₉ -C ₆ H ₄ ) O _1.5 P (OC _9.11 H _19.23 ) _1.5 . Technical examples are Naugard P, Mark CH300, Mark CH301, Mark CH302 and Mark CH55 (manufactured by Chemtura Corp. USA). The organic phosphites may be used in an amount of, for example, 0.01 to 10, preferably 0.05 to 5, and especially 0.1 to 3, parts by weight, based on 100 parts by weight of PVC.

A stabilizer system according to the invention may contain the described phosphite compounds in an amount of up to about 30% by weight, in particular up to about 10% by weight.

Sterically hindered amines (HALS)

worin A und V unabhängig voneinander C₁-₈-Alkyl-, C₃-₈ Alkenyl-, C₅-₈ -Zykloalkyl-, oder C₇-₉ -Phenylalkyl- sind, oder zusammen gegebenenfalls durch O, NH oder CH₃-N unterbrochenes C₂-₅ -Alkylen bilden, oder um ein zyklisches sterisch gehindertes Amin, insbesondere eine Verbindung aus der Reihe der Alkyl- bzw. Polyalkylpiperidine, vor allem der Tetramethylpiperidine enthaltend die Gruppe

The sterically hindered amines are generally compounds containing the group

wherein A and V are independently C ₁ - ₉ phenylalkyl, or together optionally replaced by O, NH or CH ₃ - ₈ alkyl, C _3-8 alkenyl, C _5-8 -Zykloalkyl-, or C ₇ - N interrupted C ₂ - ₅ -alkylene form, or a cyclic sterically hindered amine, in particular a compound from the series of alkyl or polyalkylpiperidines, especially the tetramethylpiperidines containing the group

Examples of such polyalkylpiperidine compounds are the following (in the case of the oligomeric or polymeric compounds, n and r are in the range from 2 to 200, preferably in the range from 2 to 10, in particular from 3 to 7). An extensive list of such compounds can be found in EP 0 796 888 B1 ,

The content of a stabilizer system according to the invention to ester. hindered amines, for example, is about 0.01 to about 10 wt .-%.

glycidyl

wobei diese direkt an Kohlenstoff, Sauerstoff-, Stickstoff- oder Schwefelatome gebunden ist, und worin entweder R₃ und R₅ beide Wasserstoff sind, R₄ Wasserstoff oder Methyl und n = 0 ist, oder worin R₃ und R₅ zusammen -CH₂-CH₂- oder -CH₂-CH₂-CH₂- bedeuten, R₄ dann Wasserstoff und n = 0 oder 1 ist.Examples of glycidyl compounds are compounds having the glycidyl group:

wherein this is bonded directly to carbon, oxygen, nitrogen or sulfur atoms, and wherein either R ₃ and R _{5 are} both hydrogen, R _{4 is} hydrogen or methyl and n = 0, or wherein R ₃ and R ₅ together are -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -, then R ₄ is hydrogen and n = 0 or 1.

I) Glycidyl and β-methylglycidyl esters obtainable by reacting a compound having at least one carboxyl group in the molecule and epichlorohydrin or glycerol dichlorohydrin or β-methyl epichlorohydrin. The reaction is conveniently carried out in the presence of bases.

As compounds having at least one carboxyl group in the molecule, aliphatic carboxylic acids can be used. Examples of these carboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid, acrylic and methacrylic acid, caproic, caprylic, pelargonic, lauric, myristic, palmitic and stearic acid.

However, it is also possible to use cycloaliphatic carboxylic acids, for example cyclohexane carboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.

It is also possible to use aromatic carboxylic acids, for example benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.

Also, carboxyl-terminated adducts, for. Trimellitic acid and polyols such as glycerin or 2,2-bis (4-hydroxycyclohexyl) propane. Other usable in the context of this invention epoxy compounds can be found in EP 0 506617 ,

II) glycidyl or (β-methylglycidyl) ethers obtainable by reacting a compound having at least one free alcoholic hydroxy group and / or phenolic hydroxy group and a suitably substituted epichlorohydrin under alkaline conditions, or in the presence of an acidic catalyst and subsequent alkali treatment.

Ethers of this type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol, or poly (oxypropylene) glycols, propane-1,3-diol, Butane-1,4-diol, poly (oxytetramethylene) -glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1- Trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, as well as polyepichlorohydrins, butanol, amyl alcohol, pentanol, and monofunctional alcohols such as isooctanol, 2-ethylhexanol, isodecanol and C ₇ -C ₉ alkanol and C ₉ -C ₁₁ alkanol mixtures.

However, they are also derived, for example, from cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) -propane or 1,1- Bis- (hydroxymethyl) -cyclohex-3-enes or they have aromatic Nuclei such as N, N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamino) diphenylmethane.

The epoxy compounds may also be derived from mononuclear phenols, such as phenol, resorcinol or hydroquinone; or are based on polynuclear phenols such as bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane, 4,4'-dihydroxydiphenylsulfone or condensation products of phenols with formaldehyde such as phenol novolacs obtained under acidic conditions.

Further possible terminal epoxides are, for example: glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, 2-biphenylglycidyl ether, N- (2,3-epoxypropyl) phthalimide and 2,3-epoxypropyl-4-methoxyphenyl ether.

III) (N-glycidyl) compounds obtainable by dehydrochlorinating the reaction products of epichlorohydrin with amines containing at least one amino hydrogen atom. These amines are, for example, aniline, N-methylaniline, toluidine, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane, but also N, N , O-triglycidyl-m-aminopheno 1 or N, N, O-triglycidyl-p-aminophenol.

The (N-glycidyl) compounds also include N, N'-di-, N, N ', N "-tri- and N, N', N", N "'- tetraglycidyl derivatives of cycloalkylene ureas, such as ethyleneurea or 1,3-propyleneurea, and N, N'-diglycidyl derivatives of hydantoins, such as of 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.

IV) S-glycidyl compounds such as di-S-glycidyl derivatives derived from dithiols such as ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether.

V) Epoxy compounds having a radical of the above formula in which R 1 and R 3 together are --CH 2 --CH 2 - and n is 0 are bis (2,3-epoxycyclopentyl) ethers, 2,3-epoxycyclopentylglycidyl ethers or 1,2-bis - (2,3-epoxyzyklopentyloxy) ethane. An epoxy resin having a radical of the above formula wherein R1 and R3 together are -CH2-CH2- and n is 1 is, for example, 3,4-epoxy-6-methylcyclohexanecarboxylic acid (3 ', 4'-epoxy-6 '-methyl-cyclohexyl) -methyl ester.

1. a) flüssige Bisphenol-A-diglycidylether wie Araldit®GY 240, Araldit®GY 250, Araldit®GY 260, Araldit®GY 266, Araldit®GY 2600, Araldit®MY 790 und Epicote® 828 (BADGE);
2. b) feste Bisphenol-A-diglycidylether wie Araldit®GT 6071, Araldit®GT 7071, Araldit®GT 7072, Araldit®GT 6063, Araldit®GT 7203, Araldit®GT 6064, Araldit®GT 7304, Araldit®GT 7004, Araldit®GT 6084, Araldit®GT 1999, Araldit®GT 7077, Araldit®GT 6097, Araldit®GT 7097, Araldit®GT 7008, Araldit®GT 6099, Araldit®GT 6608, Araldit®GT 6609, Araldit®GT 6610 und Epikote® 1002;
3. c) flüssige Bisphenol-F-diglycidylether wie Araldit®GY 281, Araldit®PY 302, Araldit®PY 306 (BFDGE);
4. d) feste Polyglycidylether von Tetraphenylethan wie CG Epoxy Resin®0163;
5. e) feste und flüssige Polyglycidylether von Phenolformaldehyd Novolak wie EPN 1138, EPN 1139, GY 1180, PY 307 (NODGE);
6. f) feste und flüssige Polyglycidylether von o-Kresolformaldehyd Novolak wie ECN 1235, ECN 1273, ECN 1280, ECN 1299 (NODGE);
7. g) flüssige Glycidylether von Alkoholen wie Shell Glycidylether® 162, Araldit®DY 0390, Araldit®DY 0391;
8. h) flüssige und feste Glycidylester von Karbonsäuren wie Shell Cardura® E Terephthalsäureester, Trimellithsäureester sowie deren Mischungen Araldit®PY 284 und Araldit® P811;
9. i) feste heterozyklische Epoxidharze (Triglycidylisocyanurat) wie Araldit® PT 810;
10. j) flüssige zykloaliphatische Epoxidharze wie Araldit®CY 179;
11. k) flüssige N,N,O-Triglycidylether von p-Aminophenol wie Araldit®MY 0510;
12. l) Tetraglycidyl-4-4'-methylenbenzamin oder N,N,N',N'-Tetraglycidyldiamino-phenylmethan wie Araldit®MY 720, Araldit®MY 721.

Suitable terminal epoxides are, for example:

1. a) liquid bisphenol A diglycidyl ethers such as Araldit® GY 240, Araldit® GY 250, Araldit® GY 260, Araldit® GY 266, Araldit® GY 2600, Araldit® MY 790 and Epicote® 828 (BADGE);
2. b) solid bisphenol A diglycidyl ethers such as Araldit® GT 6071, Araldit® GT 7071, Araldit® GT 7072, Araldit® GT 6063, Araldit® GT 7203, Araldit® GT 6064, Araldit® GT 7304, Araldit® GS 7004, Araldite ®GT 6084, Araldit® GT 1999, Araldit® GT 7077, Araldit® GT 6097, Araldit® GT 7097, Araldit® GT 7008, Araldit® GT 6099, Araldit® GS 6608, Araldit® GS 6609, Araldit® GT 6610 and Epikote ® 1002;
3. c) liquid bisphenol F diglycidyl ethers such as Araldit®GY 281, Araldit®PY 302, Araldit®PY 306 (BFDGE);
4. d) solid polyglycidyl ethers of tetraphenylethane such as CG Epoxy Resin® 0163;
5. e) solid and liquid polyglycidyl ethers of phenolformaldehyde novolaks such as EPN 1138, EPN 1139, GY 1180, PY 307 (NODGE);
6. f) solid and liquid polyglycidyl ethers of o-cresol formaldehyde novolac such as ECN 1235, ECN 1273, ECN 1280, ECN 1299 (NODGE);
7. g) liquid glycidyl ethers of alcohols such as Shell Glycidyl ether® 162, Araldit® DY 0390, Araldit® DY 0391;
8. h) liquid and solid glycidyl esters of carboxylic acids such as Shell Cardura® E terephthalic acid esters, trimellitic acid esters and their mixtures Araldit®PY 284 and Araldit® P811;
9. i) solid heterocyclic epoxy resins (triglycidyl isocyanurate) such as Araldit® PT 810;
10. j) liquid cycloaliphatic epoxy resins such as Araldit® CY 179;
11. k) liquid N, N, O-triglycidyl ethers of p-aminophenol such as Araldit®MY 0510;
12. l) Tetraglycidyl-4-4'-methylenebenzamine or N, N, N ', N'-tetraglycidyldiaminophenylmethane such as Araldit®MY 720, Araldit®MY 721.

Predominantly preferred are diglycidyl compounds based on ether or ester. Very particular preference is given to solid glycidyl esters of terephthalic and trimellitic acids.

Optionally, a mixture of different epoxy compounds can be used.

Epoxidized fatty acid esters

Examples of these epoxy compounds are epoxidized soybean oil, epoxidized olive oil, epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil, epoxidized corn oil, and epoxidized cottonseed oil, epoxidized rapeseed oil, epoxidized palm oil, epoxidized coconut oil and epoxidized butyl and octyl oleate or epoxidized linoleol esters.

The concentration range for epoxy compounds is preferably 0.5 to 5.0 phr.

antioxidants

These include sterically hindered phenols, such as alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol, alkylthiomethylphenols, e.g. 2,4-dioctylthiomethyl-6-tert-butylphenol, alkylated hydroquinones, e.g. 2,6-di-tert-butyl-4-methoxyphenol, hydroxylated thiodiphenyl ethers, e.g. 2,2'-thio-bis (6-tert-butyl-4-methylphenol), alkylidene bisphenols, e.g. 2,2'-methylenebis (6-tert-butyl-4-methylphenol), benzyl compounds, e.g. 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ethers, hydroxybenzylated malonates, e.g. Dioctadezyl 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, hydroxybenzyl aromatics, e.g. B. 1, 3, 5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, triazine compounds, e.g. 2,4-bis-octyl mercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) 1,3,5-triazine, phosphonates and phosphonites, e.g. Dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, acylaminophenols, e.g. 4-Hydroxylauric acid anilide, esters of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid, beta- (3,5-Dicyclohexyl-4-hydroxyphenyl) propionic acid, esters of 3,5-di-tert-butyl-4-hydroxy-phenylacetic acid with monohydric or polyhydric alcohols, amides of β- (3,5-di-tert -butyl-4-hydroxyphenyl) -propionic acid, eg N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, vitamin E (tocopherol) and derivatives, and D, L-ascorbic acid. The antioxidants may be used in an amount of, for example, 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of PVC become.

UV absorber and light stabilizer

Examples are 2- (2'-hydroxyphenyl) -benzotriazoles, e.g. 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2-hydroxybenzophenones, esters of optionally substituted benzoic acids, e.g. 4-tert-butylphenyl salicylate, phenyl salicylate, acrylates, nickel compounds, oxalic acid diamides, e.g. 4,4'-di-octyloxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyl-oxanilide, 2- (2-hydroxyphenyl) -1,3,5-triazines, e.g. 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, sterically hindered amines based on tetramethylpiperidine or tetramethylpiperazinone or tetramethylmorpholinone, eg Bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate and benzoxazinones such as 1,4-bis-benzoxazinonyl- benzene.

Optical brighteners

Examples of these are bis-benzene (1,4) -oxazoles, phenylcoumarins and bis-styrylbiphenyls such as 4-methyl-7-diethylaminocoumarin, 3-phenyl-7- (4-methyl-6-butoxybenzoxazole) -coumarin, 4 4'-bis (benzoxazol-2-yl) stilbene and 1,4-bis (-benzoxazol-2-yl) -naphthalene. Preference is given to solutions of optical brighteners in a plasticizer, for example DOP.

antistatic agents

Antistatic agents are classified into nonionic (a), anionic (b), cationic (c) and amphoteric (d) classes. To (a) include fatty acid ethoxylates, fatty acid esters, ethoxylated fatty alkylamines, fatty acid diethanolamides and ethoxylated phenols and alcohols, and polyglycol monofatty acid esters. To (b) include alkali fatty bisulfonates and phosphoric acid bis-fatty alcohol ester alkali salts. (C) includes fatty alkyl quaternary ammonium salts and (d) includes fatty alkyl betaines and fatty alkyl imidazoline betaines. Individual preferred compounds are lauric diethanolamide, myristyl diethanolamine, Na octadecyl sulfonate and Na bis-octadecyl phosphate.

pigments

Also suitable as part of the stabilizer system according to the invention are pigments. Suitable substances are known to the person skilled in the art. Examples of inorganic pigments are TiO ₂ , zirconia-based pigments, BaSO ₄ , zinc oxide (zinc white) and lithopone (zinc sulfide / barium sulfate), carbon black, carbon black-titanium dioxide mixtures, iron oxide pigments, Sb ₂ O ₃ , (Ti, Ba, Sb) O ₂ , Cr ₂ O ₃ , spinels such as cobalt blue and cobalt green, Cd (S, Se), ultramarine blue. Organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketo-pyrrolopyrrole pigments and anthraquinone pigments. Preferably, TiO _{2 is} also in micronized form. A definition and further descriptions can be found in the " Handbook of PVC Formulating, EJWickson, John Wiley & Sons, New York, 1993 ,

biocides

As biocides are to be named: isothiazolin-3-one derivatives, such as, 2-n-octyl-4-isothiazolin-3-one (OIT) and 4,5-dichloro-2-n-octyl-4-isothiazolin-3 -on (DCOIT), Ag-Zn zeolite, N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide, 2,3,5,6-tetrachloro-4- (methyl sulphonyl) pyridine, 10,10'-oxybisphenoxarsine (OBPA), quaternary ammonium and phosphonium salts, 3-iodo-2-propynyl-butylcarbamate (IPBC), benzimidazole-2-carbamic acid methyl ester, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, zinc bis-2-pyridinethiolate -Oxides (zinc pyrithione) and 1,2-benzisothiazolin-3-one, N-butylbenzisothiazolin-3-one and 2- (4-thiazolyl) benzimidazole (thiabendazole).

fillers

Fillers to be mentioned are calcium carbonate, dolomite, calcium sulfate, talc, kaolin, mica, feldspar, nepheline, syenite, wollastonite, barium sulfate, barite, aluminum hydroxide, magnesium hydroxide, carbon black and graphite.

propellant

Propellants are e.g. organic azo and hydrazo compounds, tetrazoles, oxazines, isatric anhydride, N-methylisatinic anhydride, as well as soda and sodium bicarbonate. Preference is given to azodicarbonamide and sodium bicarbonate and mixtures thereof. Very particular preference is given to isatric anhydride or N-methylisatinic anhydride, especially in soft PVC or semi-hard PVC.

lubricant

A stabilizer system according to the invention may further contain lubricants.
Suitable lubricants are, for example: montan waxes, fatty acid esters, PE and PP waxes, amide waxes, chloroparaffins, glycerol esters or alkaline earth metal soaps, furthermore fatty ketones, and combinations thereof, as in PS - EP 0,259,783 A1 listed.

A stabilizer system according to the invention may contain the lubricants described in an amount of up to about 70% by weight, in particular up to about 40% by weight.

softener

1. (i) Phthalsäureester wie bevorzugt Di-2-ethylhexyl-, Di-iso-nonyl- und Di-iso-dezylphthalat, die auch unter den gebräuchlichen Abkürzungen DOP (Dioktylphthalat, Di-2-ethylhexyl-phthalat), DINP (Diisononylphthalat), DIDP (Diisodezylphthalat) bekannt sind
2. (ii) Ester aliphatischer Dikarbonsäuren, insbesondere Ester von Adipin-, Azelain- und Sebazinsäure, bevorzugt Di-2-ethylhexyladipat und Di-iso-oktyladipat
3. (iii) Trimellitsäureester, beispielsweise Tri-2-ethylhexyltrimellitat, Tri-iso-dezyltri-mellitat (Gemisch), Tri-iso-tridezyltrimellitat, Tri-iso-oktyltrimellitat (Gemisch) sowie Tri-C₆-C₈-alkyl, Tri-C₆-C₁₀-alkyl-, Tri-C₇-C₉-alkyl- und Tri-C₉-C₁₁-alkyl-trimellitate; gebräuchliche Abkürzungen sind TOTM (Trioktyltrimellitat, Tri-2-ethylhexyl-trimellitat), TIDTM (Triisodezyltrimellitat) und TITDTM (Triisotridezyltrimellitat)
4. (iv) Epoxyweichmacher; in der Hauptsache sind das epoxidierte ungesättigte Fettsäuren z.B. epoxidiertes Sojabohnenöl
5. (v) Polymerweichmacher: Die gebräuchlichsten Ausgangsmaterialien für ihre Herstellung sind Dikarbonsäuren wie Adipin-, Phthal-, Azelain- und Sebazinsäure; Diole wie 1,2-Propandiol, 1,3-Butandiol, 1,4-Butandiol, 1,6-Hexandiol, Neopentylglykol und Diethylenglykol, (s. ADMEX^®-Typen der Velsicol Corp. und PX-811 der Asahi Denka)
6. (vi) Phosphorsäureester: Eine Definition dieser Ester ist im weiter vom genannten "TASCHENBUCH der Kunststoffadditive " Kapitel 5.9.5, SS. 408 - 412, zu finden. Beispiele für solche Phosphorsäureester sind Tributylphosphat, Tri-2-ethylbutylphosphat, Tri-2-ethylhexylphosphat, Trichlorethylphosphat, 2-Ethyl-hexyl-di-phenylphosphat, Kresyldiphenylphosphat, Resorzin-bis-diphenylphosphat, Triphenylphosphat, Trikresylphosphat und Trixylenylphosphat; bevorzugt sind Tri-2-ethylhexyl-phosphat sowie Reofos^® 50 und 95 (Ciba Spezialitätenchemie)
7. (vii) Chlorierte Kohlenwasserstoffe (Paraffine)
8. (viii) Kohlenwasserstoffe
9. (ix) Monoester, z.B. Butyloleat, Phenoxyethyloleat, Tetrahydrofurfuryloleat und Alkylsulfonsäureester
10. (x) Glykolester, z.B. Diglykolbenzoate
11. (xi) Zitronensäureester, z.B. Tributylzitrat und Acetyltributylzitrat wie in PS - WO 02/05206 beschrieben
12. (xii) Perhydrophthal-, -isophthal- und -terephthalester sowie Perhydroglykol- und diglykolbenzoatester; bevorzugt ist Perhydro-diisononylphthalat (Hexamoll^® DINCH - Hersteller BASF) wie in PS - DE 197.56.913 A1 , DE 199.27.977 A1 , DE 199.27.978 A1 und DE 199.27.979 A1 beschrieben.
13. (xiii) Rizinussöl basierte Weichmacher (Soft-N-Safe^®, Hersteller Fa. DANISCO)
14. (xiv) Terpolymere Keton-Ethylen-Ester Elvaloy^® KEE, (Elvaloy^® 741, Elvaloy^® 742, Hersteller Fa. DuPont)

Also useful as additives for the stabilizer system of the present invention are organic plasticizers. Suitable organic plasticizers are, for example, those from the following groups:

1. (i) phthalic acid esters, such as, preferably, di-2-ethylhexyl, di-isononyl and di-iso-decyl phthalate, which are also used under the common abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate), DIDP (diisodiacyl phthalate) are known
2. (Ii) esters of aliphatic dicarboxylic acids, especially esters of adipic, azelaic and sebacic acid, preferably di-2-ethylhexyl adipate and di-iso-octyl adipate
3. (iii) trimellitic acid esters, for example tri-2-ethylhexyl trimellitate, triisodecyltrimellitate (mixture), triisopropyltrimellitate, triisoctyl trimellitate (mixture) and also tri-C ₆ -C ₈ -alkyl, tri-iso-tri-octyl trimellitate C ₆ -C ₁₀ alkyl, tri C ₇ -C ₉ alkyl and tri C ₉ -C ₁₁ alkyl trimellitate; common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIDTM (tri-ethylbenzyl trimellitate) and TITD ™ (tri-isotride-cyl trimellitate)
4. (iv) epoxy plasticizer; in the main, the epoxidized unsaturated fatty acids are, for example, epoxidized soybean oil
5. (v) polymer plasticizer: The most common starting materials for their preparation are dicarboxylic acids such as adipic, phthalic, azelaic and sebacic acids; Diols such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol, (s. AdmEx ^® grades of Velsicol Corp. and PX-811 of Asahi Denka)
6. (vi) Phosphoric Acid Esters: A definition of these esters can be found in the "TASCHENBUCH der Kunststoffadditive" chapter 5.9.5, pp. 408-412. Examples of such phosphoric acid esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethyl-hexyl-di-phenyl phosphate, cresyl diphenyl phosphate, resorcin-bis-diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate; preferred are tri-2-ethylhexyl phosphate and Reofos ^® 50 and 95 (Ciba Specialty Chemicals)
7. (vii) chlorinated hydrocarbons (paraffins)
8. (viii) hydrocarbons
9. (ix) monoesters, eg butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkyl sulfonic acid esters
10. (x) Glycol esters, eg diglycol zoates
11. (xi) citric acid esters, eg tributyl citrate and acetyltributyl citrate as in PS - WO 02/05206 described
12. (xii) perhydrophthalic, isophthalic and terephthalic esters, and perhydroglycol and diglycol zoate esters; preferably perhydro-diisononyl (Hexamoll ^® DINCH - manufacturer BASF) as in PS - DE 197.56.913 A1 . DE 199.27.977 A1 . DE 199.27.978 A1 and DE 199.27.979 A1 described.
13. (xiii) castor oil-based plasticizer (Soft-N-Safe ^®, manufacturer. DANISCO)
14. (xiv) terpolymers ketone ethylene ester Elvaloy ^® KEE, (Elvaloy ^® 741, Elvaloy ^® 742, manufacturer Messrs. Du Pont)

A definition of these plasticizers and examples of such are in " TASCHENBUCH der Kunststoffadditive ", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd ed., 1989, chapter 5.9.6, pages 412-415 , as in " PVC Technology ", WV Titov, 4th Ed., Elsevier Publ., 1984, pp. 165-170 specified. It can also be used mixtures of different plasticizers. The plasticizers may contain in an amount of, for example, up to about 99.5% by weight, more preferably up to about 30% by weight, up to about 20% by weight or up to about 10% by weight. In a preferred embodiment of the present invention, the lower limit for the described plasticizers as part of the stabilizer systems according to the invention about 0.1 wt .-% or more, for example about 0.5 wt .-%, 1 wt .-%, 2 wt. -% or 5 wt .-%.

Flame retardants and smoke reducers

Suitable flame retardants in particular in soft PVC are preferably: aluminum hydroxide, magnesium hydroxide and oligomeric or polymeric Phosphorsäurephenolester. Very particular preference is given to nanoclay-based flame retardants (organomodified clay; Beyer, G. Journal of Fire Sciences, 2007, 25, 65-78 ). As a smoke reducer, preference is given to using inorganic substances based on zinc oxide or tin oxide or as zinc (hydroxo) stannate, ammonium molybdate, zinc molybdate and zinc borate or magnesium-zinc complex oxides of the formula (Mg, Zn) O ( WO 2008/023249 ).

A stabilizer system according to the invention may contain the described flame retardants in an amount of up to about 70% by weight, in particular up to about 50% by weight.

Definitions and examples of other additives such as impact modifiers and processing aids, gelling agents, biocides, metal deactivators, antifogging agents and compatibilizers are described in " Handbuch der Kunststoffadditive ", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd ed., 1989, as well as 4th edition 2001 and in " Handbook of Polyvinyl Chloride Formulating "EJ Wickson, J. Wiley & Sons, 1993 , as in " Plastics Additives "G. Pritchard, Chapman & Hall, London, 1st ed., 1998 , Impact modifiers are further described in detail in " Impact Modifiers for PVC ", JT Lutz / DL Dunkelberger, John Wiley & Sons, 1992 ,

Another object of the invention are compositions containing a halogen-containing polymer and a stabilizer system according to the invention.

In these compositions, the components (A) + (B), (A) + (C) and (A) + (B) + (C) for the purpose of stabilization in the halogen-containing polymer are useful in the following concentration ranges: Prefers: (A) 0.01 1 to 30 parts by weight (B) 0.001 to 10 parts by weight (C) 0.01 to 10 parts by weight Particularly preferred: (A) 0.05 to 15 parts by weight (B) 0.01 to 5.0 parts by weight (C) 0.01 to 5.0 parts by weight Very particularly preferred: (A) 0.1 to 10 parts by weight (B) 0.01 to 3.0 parts by weight (C) 0.01 to 3.0 parts by weight based on 100 parts by weight of halogen-containing polymer.

In addition, it is preferred that the compounds of the formula (A) are present in an amount of from 0.01 to 3.0 phr, preferably from 0.05 to 1.5 phr and more preferably from 0.1 to 1.0 phr.

In addition, the composition according to the invention may of course contain further compounds which are mentioned above as constituents of the stabilizer system according to the invention.

Another object of the present application is therefore a composition which further comprises at least one compound from the substance classes of zeolites, hydrotalcites, dawsonites and calcium carbonato-hydroxodialuminate; Catena μ-2,2 ', 2 "nitrilotrisethanol perchlorato (triflato) sodium or lithium inner complexes or lithium or sodium perchlorates (triflates) in dissolved or supported form; fatty acid calcium or zinc salts (calcium or zinc soaps); Polyols and sugar alcohols and / or 1,4-dihydropyridine derivatives (DHP); linear or cyclic β-diketones or β-ketoesters and their calcium, magnesium or zinc salts; Phosphorous acid esters (phosphites) and hindered amines; Glycidyl compounds and epoxidized fatty acid esters; Antioxidants, UV absorbers and optical brighteners; Pigments and biocides; Fillers and blowing agents; Lubricants and plasticizers; Flame retardants and smoke reducers; Having impact modifiers and processing aids.

Examples of the halogen-containing polymers to be stabilized are chlorine-containing polymers, in particular those of vinyl chloride, which is very particularly preferred, and vinylidene chloride, vinyl resins containing vinyl chloride units in their structure, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, especially vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; Vinylidene chloride polymers and copolymers thereof with vinyl chloride and other polymerizable compounds; Polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and alpha-substituted acrylic acid; Polymers of chlorinated styrenes, for example dichlorostyrene; Chlorinated rubbers; chlorinated polymers of ethylene; Polymers and post-chlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride, chlorinated natural and synthetic rubbers, and Mixtures of the above polymers with each other or with other polymerizable compounds. In the context of this invention, PVC also means copolymers of vinyl chloride with polymerizable compounds such as acrylonitrile, vinyl acetate or ABS, which may be suspension, bulk or emulsion polymers.

Preference is given to a PVC homopolymer, also in combination with polyacrylates or polymethacrylates.

Also suitable are graft polymers of PVC with EVA, ABS and MBS, as well as graft polymers of PVC with PMMA. Preferred substrates are also mixtures of the abovementioned homopolymers and copolymers, in particular vinyl chloride homopolymers, with other thermoplastic or / and elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and Polylactones, in particular from the group ABS, NBR, NAR, SAN and EVA. The related abbreviations for the copolymers are familiar to the person skilled in the art and mean the following: ABS acrylonitrile-butadiene-styrene; SAN styrene-acrylonitrile; NBR acrylonitrile-butadiene; NAR acrylonitrile acrylate; EVA ethylene vinyl acetate. In particular, styrene-acrylonitrile copolymers based on acrylate (ASA) into consideration. Preferred components in this context are polymer compositions which contain as components (i) and (ii) a mixture of 25-75% by weight of PVC and 75-25% by weight of the copolymers mentioned. Of particular importance as a component are compositions of (i) 100 parts by weight of PVC and (ii) 0-300 parts by weight of ABS and / or SAN-modified ABS and 0-80 parts by weight of the copolymers NBR, NAR and / or EVA, but especially EVA.

Also suitable for stabilization in the context of this invention are in particular recyclates of chlorine-containing polymers, which are the polymers described in greater detail above, which have suffered damage as a result of processing, use or storage. Particularly preferred is PVC recyclate. Another use of the stabilizer combinations according to the invention is that antistatic properties can be imparted to the finished article made of rigid or soft PVC. In this way it is possible to reduce the use of expensive antistatic agents. Preferred for this application is soft PVC or semi-rigid PVC.

Another object of the invention are articles such as consumer (commodities) containing a composition of the invention and the halogen-containing polymer.

Preference is also the use of consumer goods, which are characterized by a special fine foam structure. This applies to hard, soft and semi-hard PVC. This aspect is particularly important for wallpapers and floors made of soft PVC. Normally, heavy metal compounds such as Zn or Sn stabilizers are required as kickers to obtain a fine foam. Surprisingly, it has been found that TEAP inner complexes exert a kicker effect on isatinic acid or N-methylisatinic anhydride, which ensures the achievement of a fine foam structure.

It is also surprising that the electrical resistance properties of a consumer article containing TEA inner complexes as a component are drastically improved, which proves to be favorable in particular in cable and insulator production and in semiconductor applications.

Furthermore, these products (mainly cables), when stabilized zinc-free, perform better when stored in water, since the formulations do not contain zinc soaps and thus do not produce zinc chloride during processing, which deteriorates the electrical values after migration to the plastic surface.

In addition, in zinc-sensitive applications, zinc-containing fungicides may be added primarily in soft PVC (e.g., films, roofing membranes) in dire need of biocidal equipment, which is otherwise severely limited by the use of calcium-zinc stabilizers.

The co-usable compounds as well as the halogen-containing polymers are generally known to the person skilled in the art and are described in detail in " HANDBUCH DER KUNSTOFFADDIVE ", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd ed., 1989 and 4th edition 2001 , in DE 197.41.778 A1 and EP 0.967.245 A1 which is hereby incorporated by reference.

The stabilization according to the invention is particularly suitable both for halogen-containing polymer compositions that are not plasticized or plasticizer-free or substantially plasticizer-free compositions, as well as for plasticized compositions. Particular preference is given to applications in rigid PVC or PVC semi-hard.

The compositions according to the invention are particularly suitable, in the form of hard formulations, for hollow bodies (bottles), packaging films (deep-drawn films), blown films, "crash pad" films (automobiles), pipes, foams, heavy profiles (window frames), light-wall profiles, building profiles, Foils, blister packs (also made after the Luvitherm method), profiles, sidings, fittings, office films, margarine cups, chocolate packaging and apparatus housings, insulators, computer housings and components of household appliances as well as for electronic applications, in particular in the semiconductor sector. These are particularly suitable for the production of window profiles with high whiteness and surface gloss.

Preferred other compositions in the form of semi-hard and soft formulations are for wire sheathing, cable insulation, decorative films, roofing foils, foams, agricultural films, hoses, sealing profiles, flooring, wallpaper, automotive parts, soft films, injection molded parts (blow molding), office films and Foils suitable for inflatable halls. Examples of the use of the compositions according to the invention as plastisols are toys (rotational molding), artificial leather, flooring, textile coatings, wallpaper, coil coatings and underbody protection for motor vehicles. Examples of sintered PVC applications of the compositions according to the invention are slush, slush mold and coil coatings and in E-PVC for films produced by the Luvithermverfahren. For details see " PLASTICS MANUAL PVC ", Volume 2/2, W. Becker / H. Braun, 2nd ed., 1985, Carl Hanser Verlag, pp. 1236-1277 ,

Another object of the present invention is the use of a stabilizer system according to the invention for stabilizing a halogen-containing polymer and the use of a composition according to the invention for producing an article according to the invention.

• Zusetzen eines erfindungsgemäßen Stabilisatorsystems zu dem halogenhaltigen Polymer.

Another object of the present invention is a method for stabilizing a halogen-containing polymer, comprising the step

• Adding a stabilizer system according to the invention to the halogen-containing polymer.

Experimental part I. Preparation of the rolled skins:

The dry mixes prepared according to Table 1.1 (R-1 and R-2) and 2.1 (R-3, R-4, R-5 and R-6) are tested on a Collin laboratory bench mill (Model: W100E, BJ: 2005, Fa COLLIN) each 5 minutes (roll diameter: 110 mm, 10 rpm, friction: -10%) plasticized at the indicated temperature. The resulting films (thickness 0.3 mm) are fed to further measurements.

II. Performance of Dehydrochlorination Measurements (DHC):

The DHC is a measure of the HCl elimination of PVC that occurs under thermal stress. The split-off hydrochloric acid is charged with nitrogen gas into a receiver with dist. Rinsed water and there measured the increase in conductivity in microsiemens per centimeter (μS / cm). Key figures are the associated minute values [Min], which are summarized in tabular form. The longer the time interval at certain temperatures to reach a certain conductivity, the more thermostable the PVC sample is.
Device type: PVC Thermomat 763 (Metrohm)
The measurements are carried out according to DN 53381 Part 1, Method B: Conductivity measurement. Parameter: sample weight: 500 ± 0,5mg (rolled skin chips) Temperature: ° C (as indicated in the examples) flow: 71 / h (nitrogen 5.0) Absorptionsvol .: 60ml (deionized water) Evaluation: t ₁₀ , t ₅₀ and t ₂₀₀ (conductivity of 10, 50 and 200 μS / cm - in minutes)

III. Performing the static heat test (SHT):

Test strips (15mm x 15mm) are cut out of the skin skins manufactured according to I. These are loaded in a METRASTAT test oven IR 700 (DR. STAPFER GmbH, Dusseldorf) at the indicated temperature until significant discoloration. The YI value (yellowness index) according to DIN 53381 is then determined using a Spectro-Guide colorimeter (BYK-GARDNER) and compared with the YI value of the unloaded rolled skin (zero minute value). The results are summarized in tabular form. The smaller the YI value at a given time, the better the color behavior.

Example 1: (soft PVC, cable recipe):

The following dry blends were prepared (Table 1.1) - weight in parts by weight: <B> Table. 1.1: Formulations </ b> components (R-1) (R-2) PVC (Vinnolit S4170), K value = 70 100 100 Plasticizer ¹⁾ (DINP) 50 50 Chalk ²⁾ (Polcarb 50 SV) 50 50 Antioxidant ³⁾ (BPA) 0.43 0.43 Zinc stearate ⁴⁾ - 1.0 DMAU ⁵⁾ (B2) 0.4 - TEAP 50 ⁶⁾ 0.32 - Calcium magnesium dioxide ⁷⁾ (A3) 2.57 - Sorbacid 911 ⁸⁾ - 2.57 Total amount of stabilizer 3.72 4.0 ¹⁾ Diisononyl phthalate, ex BASF
2) ex IMERYS
3) Bisphenol A, ex ALDRICH
4) ex ALDRICH
5) 6-amino-1,3-dimethyluracil, ex ALDRICH
6) Catena μ-2,2 ', 2''- nitrilotrisethanol perchlorato sodium (50% active substance, own product)
7) CeM-iX_115, ex BENE_FIT Systems GmbH & Co. KG, Hirschau, DE
8) ex SOUTH CHEMISTRY (corresponds to Alcamizer 1)

Formulation (R-1) is according to the invention (zinc-free) - since (A3) + (B2) containing, the comparison (R-2) is a non-inventive zinc-based stabilizer.

The formulations (R-1) and (R-2) have the following DHC values (Table 1.2): <B> Table. 1.2: DHC values </ b> (200 ° C) according to II, <b> rolling skins: </ b> 190 ° C according to I conductivity (R-1) (R-2) [S / cm] [Min] [Min] 10 148 97 50 176 116 200 244 147 Comparing (R-1) with (R-2), a significant improvement can be observed compared to the zinc-containing formulation (R-2) which is not according to the invention (transition to higher minute values), ie the thermal stability has been markedly improved.

The testing of the formulations (R-1) and (R-2) showed the following result in SHT (Table 1.3): <B> Table. 1.3: SHT </ b> (190 ° C) according to III Time [min] (R-1) [YI] (R-2) [YI] 3 23.5 25.0 6 23.4 26.5 9 23.5 27.0 12 23.7 27.6 15 24.0 28.1 18 24.1 28.2 21 24.4 28.7 24 24.7 29.7 27 25.1 30.1 30 25.2 30.6 33 25.5 31.4 36 26.0 32.1 39 26.4 33.1 42 26.9 33.6 45 27.6 34.9 48 28.3 36.0 51 29.0 36.4 54 30.0 37.2 57 31.1 37.5 60 31.7 39.6

As can be seen, the combination (R-1) according to the invention shows improved color values in relation to the initial color AF (up to 20 min.) Compared to the zinc-containing formulation (R-2) not in accordance with the invention, color retention FH (up to 40 min.) And long-term stability. LZ (up to 60 min.). This means that the erfingungsgemäße formulation (R-1) of the non-inventive zinc-containing formulation (R-2) in the efficacy is clearly superior, although the amount of stabilizer in (R-1) with 3.72 parts is significantly lower than in (R -2) with 4.0 parts.

Example 2: (hard PVC, window recapture):

The following dry mixes were prepared (Table 2.1): <B> Table. 2.1: Formulations </ b> components (R-3) (R-4) (R-5) (R-6) PVC (Vinnolit S3268) 94 94 94 94 K value = 68 PVC ⁹⁾ (Vinnolit K 707) 12 12 12 12 Chalk (Omyalite 95T) 6 6 6 6 Titanium dioxide (Kronos 2220) 4 4 4 4 Lubricant ¹⁰⁾ (LOXIOL G60) 0.6 0.6 0.6 0.6 Lubricant ¹¹⁾ (LOXIOL G22) 0.1 0.1 0.1 0.1 Lubricant ¹²⁾ (Licowax WE 4 P) 0.2 0.2 0.2 0.2 Lubricant ¹³⁾ (Licowax PE 520) 0.2 0.2 0.2 0.2 Irganox 1010 ¹⁴⁾ 0.15 0.15 0.15 0.15 DMAU ⁵⁾ (B2) 0.4 - - - TEAP 50 ⁶⁾ 0.32 - - - THEIC ¹⁵⁾ (B1) 0.3 0.31 0.31 0.31 Calcium magnesium dioxide ⁷⁾ (A3) 1.6 - 0.82 0.62 Alcamizer 1 ¹⁶⁾ (C) - 0.82 - 0.20 Calcium acetylacetonate ¹⁷⁾ - 0.3 0.3 0.3 Zinc laurate ¹⁸⁾ - 0.75 0.75 0.75 Calcium stearate ¹⁹⁾ 0.6 0.68 0.68 0.68 ⁹⁾ Polyacrylate-based (PA ⁾ impact modifier (PVC: PA = 1: 1)
^{10), 11)} ex COGNIS OLEOCHEMICALS
^{12), 13)} ex CLARIANT
¹⁴⁾ ex CIBA SPECIALTY CHEMISTRY
¹⁵⁾ Trishydroxyethyl isocyanurate, ex ALDRICH
¹⁶⁾ ex KYOWA CHEMICAL
¹⁷⁾ ex MCC Chemiehandel, Hamburg
^{18), 19)} ex PETER GREVEN Fettchemie

Formulation (R-3) is according to the invention and zinc-free - since (A3) + (B1) + (B2) containing. Formulations (R-5) and (R-6) are also in accordance with the invention but contain zinc - since (A3) + (B1) or (A3) + (B1) + (C) containing. The non-inventive comparison (R-4) is also zinc-containing. (R-4) corresponds in composition to a commercial calcium-zinc stabilizer.

The formulations (R-3) to (R-6) show the following DHC values (Table 2.2): <B> Table. 2.2: DHC values </ b> (200 ° C) according to II, <b> rolling skins: </ b> 195 ° C after 1 conductivity (R-3) (R-4) (R-5) (R-6) [S / cm] [Min] [Min] [Min] [Min] 10 75 36 47 49 50 97 40 66 62 200 119 50 80 74

As can be seen, the zinc-containing formulations (R-5) and (R-6) according to the invention show a significant improvement with respect to the 10, 50 and 200 μS / cm compared to the comparison (R-4), which is also zinc-containing -Values. The effectiveness of the zinc-free formulation (R-3) according to the invention must be judged to be excellent.

The testing of the formulations (R-3) to (R-6) showed the following result in SHT (Table 2.3): <B> Table. 2.3: SHT </ b> (190 ° C) according to III Time [min] (R-3) [YI] (R-4) [YI] (R-5) [YI] (R-6) [YI] 0 0.5 2.4 1.6 1.1 3 0.5 3.6 1.6 1.5 6 0.5 4.0 2.1 1.6 9 0.5 4.3 1.9 2.1 12 0.4 4.6 1.8 1.9 15 0.8 5.2 2.5 2.5 18 0.9 6.4 2.7 2.7 21 1.1 7.3 3.8 3.4 24 1.5 9.1 4.0 3.7 27 1.9 10.4 4.9 4.3 30 2.4 12.1 6.5 5.1 33 3.3 13.7 8.7 5.8 36 4.3 16.8 11.6 6.9 39 5.3 18.3 14.8 7.9 42 6.4 20.2 18.3 9.3 45 7.7 22.7 23.2 10.9 48 8.8 24.7 26.7 13.6 51 10 27.4 29.1 16.8 54 11.2 31.2 32.1 20.5 57 12.6 33.0 34.0 23.5 60 13.9 32.9 35.3 27.5

As can be seen, the zinc-containing formulations (R-5) and (R-6) according to the invention show a significant improvement in AF, FH and LZ (lower YI values) compared to the zinc-containing comparison (R-4) or partial replacement of Alcamizer 1 by calcium-magnesium dioxide (in equal weight) could be accomplished.

The effectiveness of the zinc-free formulation (R-3) according to the invention is excellent as in Example 1.

Claims (12)

Stabilizer system for halogen-containing polymers containing
an alkaline earth double carbonate lime of the formula (A)

(M ¹ O) _{m *} (M ² O) _{nm *} (CO ₂ ) _{o *} (H ₂ O) _p (A)

With M ¹ and M ² = different alkaline earth metals; m = 0.9 to 1.1; n = 1.9 to 2.1 and p = 0 to 2.1 or 3.9 to 4.1 and p = 0 to 4.1; o = 0 to 1.1 and at least one of the compounds selected from the group consisting of (B) and (C), wherein (B) at least one nitrogen-containing organic compound selected from the group consisting of (B1) and (B2) , where (B1) is a tert. Alkanolamine and (B2) is an enaminone or a urea and (C) an alkaline earth aluminohydroxocarbonate of the formula (C)

(M _1-x Zn _x ) _y Al ₂ (OH) _{4 +} 2yCO _{3 *} zH ₂ O (C)

with M = magnesium or / and calcium; x = 0 to 0.5; y = 2 to 8 and z = 0 to 12. Stabilizer system according to claim 1, characterized in that the alkaline earth double carbonate lime (A) is a Huntitbranntkalk of the formula (A1)

(CaO) _{m *} (MgO) _{nm *} (CO ₂ ) _o (A1)

with m = 0.9 to 1.1; n = 3.9 to 4.1 and o = 0 to 1.1. Stabilizer system according to claim 1, characterized in that the alkaline earth double carbonate lime (A) is a dolomitic lime of the formula (A2)

(CaO) _{m *} (MgO) _{nm *} (CO ₂ ) _o (A2)

with m = 0.9 to 1.1; n = 1.9 to 2.1 and o = 0 to 1.1. Stabilizer system according to claim 3, characterized in that the dolomitic lime is a calcium-magnesium dioxide of the formula CaMgO ₂ (A3) or a calcium-magnesium oxide carbonate of the formula MgO _* CaCO ₃ (A4) . Stabilizer system according to one of claims 1 to 4, characterized in that (B1) is at least one trialkanolamine, a bis-alkanol-fatty acid amine or a tris-alkanol isocyanurate. Stabilizer system according to one of Claims 1 to 5, characterized in that (B2) is at least one substituted aminouracil, an aminocrotonic acid ester or a substituted urea. Stabilizer system according to one of claims 1 to 6, characterized in that (C) is at least one magnesium or a magnesium zinc alumohydroxocarbonate (C1) or a calcium carbonate hydroxodialuminate (C2) . Stabilizer system according to one of claims 1 to 7, characterized in that at least one compound (A), (A1), (A2), (A3) and (A4) is present in coated form. A composition comprising a halogen-containing polymer and a stabilizer system according to any one of claims 1 to 8. A composition according to claim 9, characterized in that based on 100 parts by weight of halogen-containing polymer 0.05 to 10 parts by weight of the compound (A) and 0.05 to 10 parts by weight of the compound (B1) or / and (B2) and / or 0.005 to 9 parts by weight of the compound (C) are contained. A method of stabilizing a halogen-containing polymer comprising the step Adding a stabilizer system according to any one of claims 1 to 8 to the halogen-containing polymer. A commodity containing a halogen-containing polymer which is stabilized by a stabilizer system according to any one of claims 1 to 8.